US5342908A - Process for preparing halobutyl-type polymer - Google Patents

Process for preparing halobutyl-type polymer Download PDF

Info

Publication number
US5342908A
US5342908A US08/014,295 US1429593A US5342908A US 5342908 A US5342908 A US 5342908A US 1429593 A US1429593 A US 1429593A US 5342908 A US5342908 A US 5342908A
Authority
US
United States
Prior art keywords
isobutylene
methyl
solution
weight percent
halogenated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US08/014,295
Other languages
English (en)
Inventor
Akhtar Osman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polysar Rubber Corp
Arlanxeo Canada Inc
Original Assignee
Polysar Rubber Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polysar Rubber Corp filed Critical Polysar Rubber Corp
Priority to US08/014,295 priority Critical patent/US5342908A/en
Assigned to POLYSAR RUBBER CORP. reassignment POLYSAR RUBBER CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OSMAN, AKHTAR
Priority to CA002113891A priority patent/CA2113891A1/en
Priority to DE69424809T priority patent/DE69424809T2/de
Priority to EP94100941A priority patent/EP0609737B1/de
Priority to JP6027600A priority patent/JPH06287234A/ja
Priority to US08/213,658 priority patent/US5473029A/en
Publication of US5342908A publication Critical patent/US5342908A/en
Application granted granted Critical
Assigned to LANXESS INC. reassignment LANXESS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BAYER INC.
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
    • C08F210/10—Isobutene
    • C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber

Definitions

  • This invention relates to a process for the preparation of halogenated polymers analogous to halogenated butyl rubbers. More particularly, the present invention relates to a process whereby halogenated polymers analogous to halogenated butyl rubbers may be prepared directly by the copolymerization of the appropriate monomers.
  • butyl rubber as employed herein is defined to include a copolymer of a C 4 to C 6 isolefin, preferably isobutylene, and a C 4 to C 8 conjugated diolefin, preferably isoprene.
  • a preferred butyl rubber contains from about 97 to about 99.5 weight percent of isobutylene and from about 0.5 to about 3 weight percent of isoprene.
  • butyl rubber is prepared in a low temperature cationic polymerization process using Lewis acid type catalysts of which a typical example is aluminum trichloride.
  • the process used most extensively employs methyl chloride as the diluent for the reaction mixture and the polymerization is conducted at temperatures of the order of less than -90° C.
  • Methyl chloride is employed for a number of reasons, one being that it is a solvent for the monomers and aluminum trichloride catalyst and a nonsolvent for the polymer product and thus affords a slurry.
  • methyl chloride has suitable freezing and boiling points that permit, respectively, low temperature polymerization and effective separation of the methyl chloride from the product polymer and unreacted monomers.
  • a diluent which is a solvent for the polymer produced, examples of such diluents being the hydrocarbons pentane, hexane, heptane and mixtures of the aforementioned solvents with one another or with methyl chloride and/or methylene chloride.
  • Recovery of the butyl rubber is achieved by conventional techniques used to recover rubbery polymers inducing (i) contacting the polymer slurry or solution with steam and water thereby flashing off the diluent (ii) passing the aqueous slurry through a vibrating screen or rotary filter to separate the bulk of the water and (iii) passing the polymer through a tunnel drier or a series of extruders or both to completely remove all the water and occluded gases.
  • Halogenated butyl rubber which can be either brominated butyl rubber or chlorinated butyl rubber is produced by the bromination or chlorination of the aforementioned butyl rubber.
  • Brominated butyl rubber typically contains from about 1 to about 3, preferably from about i to about 2, weight percent of isoprene and from about 97 to about 99, preferably from about 98 to about 99, weight percent of isobutylene, based on the hydrocarbon content of the rubber, and from about 1 to about 4, preferably from about 1.5 to about 3, weight percent of bromine, based on the bromobutyl rubber.
  • Chlorobutyl rubber typically contains from about 1 to about 3, preferably from about 1 to about 2, weight percent of isoprene and from about 97 to about 99, preferably from about 98 to about 99, weight percent of isobutylene, based on the hydrocarbon content of the rubber and from about 0.5 to about 2.5, preferably from about 0.75 to about 1.75, weight percent of chlorine, based on the chlorobutyl rubber.
  • halogenation of the butyl rubber is carried out in a hydrocarbon solution such as hexane using elemental chlorine or bromine in a 1:1 molar ratio relative to the enchained isoprene in the butyl feedstock.
  • the solution of butyl rubber with the desired molecular weight and mole percent unsaturation in hexane may be prepared by one of two procedures; one involving dissolution of the slurry from a butyl polymerization reactor and the other involving dissolution of solid pieces of finished butyl rubber. In the former procedure the cold slurry in methyl chloride is passed into a drum containing hot liquid hexane which rapidly dissolves the fine slurry particles.
  • the methyl chloride and the unreacted monomers are flashed off for recovery and recycle and the hot solution is adjusted to the desired concentration for halogenation, typically from about 20 to about 25 weight percent butyl rubber in an adiabatic flash step.
  • halogenation typically from about 20 to about 25 weight percent butyl rubber in an adiabatic flash step.
  • bales of finished butyl rubber, chopped or ground to small pieces are conveyed to a series of agitated dissolving vessels and solutions containing from about 15 to about 20 weight percent butyl rubber are obtained in from about 1 to about 4 hours depending upon the temperature, particle size and amount of agitation.
  • the solution of butyl rubber is treated with chlorine or bromine at a temperature of from about 40° to about 65° C.
  • the chlorine being introduced as a gas or in dilute solution because of its rate of reaction with butyl rubber. Because of its lower rate of reaction bromine may be used in liquid or gaseous form.
  • the hydrochloric or hydrobromic acid generated during the halogenation is neutralized with dilute aqueous base and the aqueous layer is subsequently removed by settling.
  • Antioxidants or stabilizers are then added and the halogenated butyl rubber is then recovered in a manner similar to that used to recover butyl rubber.
  • halogenated butyl rubbers exhibit enhanced cure compatibility with highly unsaturated elastomeric materials such as natural rubber, styrene-butadiene rubbers, polybutadiene rubbers and the like relative to butyl rubber.
  • halogenated polymers with allylic halide functionality analogous to the halogenated butyl rubbers could be synthesized directly by the copolymerization of the appropriate monomers thereby leading to a reduction in costs associated with the process of halogenating butyl rubber.
  • U.S. Pat. No. 3,067,182 (Giffin to Dow) discloses the copolymerization of from about 70 to about 99 mole percent of isobutylene with about from 1 to about 30 mole percent of isopropenylbenzyl chloride, preferably the para isomer, in an inert solvent using a Friedel-Crafts catalyst and a temperature below about -50° C. to afford a uniform copolymer having reactive benzylic chloride groups.
  • U.S. Pat. NO. 3,299,020 discloses a process for the copolymerization of an olefin with an allyl halide comprising forming a first solution by mixing 5 to 25 parts of methallyl chloride and the like with 95 to 75 parts of an alkyl halide solvent such as methyl chloride, methylene chloride and ethyl chloride at a temperature of from about -5 to about -40° C.
  • an alkyl halide solvent such as methyl chloride, methylene chloride and ethyl chloride
  • a Friedel-Crafts catalyst chosen from the group consisting of boron chloride, aluminum chloride, aluminum bromide and stannic chloride until a strong colour develops; forming a second solution comprising 10 to 35 parts by weight of an olefin and 65 to 90 parts by weight of an alkyl halide; and reacting said second solution with said first solution thereby providing a copolymer of high molecular weight and a high intrinsic viscosity.
  • the copolymer obtained by the aforesaid process does not have allylic halide functionality and thus will not exhibit the enhanced cure compatibility that the halogenated butyl rubbers exhibit with highly unsaturated elastomeric materials.
  • chlorobutyl rubber may be prepared under conditions suitable for butyl rubber synthesis by copolymerizing (1) isobutylene and methallyl chloride in methyl chloride; (2) isobutylene, isoprene and methallyl chloride in methyl chloride; and (3) isobutylene and 2-chloromethyl-1,3-butadiene in methyl chloride, using aluminum chloride as catalyst. Copolymers containing up to two percent chlorine are reported to be obtained.
  • our invention provides a process for the preparation of a halogenated polymer analogous to halogenated butyl rubber comprising the steps of:
  • This invention is based upon the discovery that the copolymerization of isobutylene with an allylic halide substituted conjugated diolefin having a particular molecular structure under certain specific polymerization conditions permits the direct production of halogenated polymers with allylic halide functionality analogous to halogenated butyl rubbers.
  • the monomer charge suitable for the practice of this invention comprises from about 80 to about 95 weight percent of isobutylene and from about 5 to about 20 weight percent of a conjugated diolefin bearing an allylic halide moiety based on a total of 100 weight percent of said isobutylene and said conjugated diolefin bearing an allylic halide moiety.
  • the aforementioned conjugated diolefin is characterized in that it has the formula: ##STR5## wherein R 1 , R 2 and R 3 are selected from the group consisting of hydrogen and methyl groups and may be the same or different and X is selected from the group consisting of chlorine and bromine.
  • conjugated diolefins bearing an allylic halide moiety that are suitable for use in the present invention include 2-chloromethyl-4-methyl-1,3-pentadiene, 2-bromomethyl-4-methyl-1,3-pentadiene,2-chloromethyl-3, 4-dimethyl-1,3-pentadiene,2-chloromethyl1,3-butadiene and 2-bromomethyl-1,3-butadiene,2-chloromethyl-4-methyl-1,3-pentadiene, 2-bromomethyl-4-methyl-1, 3-pentadiene being preferred, and 2-chloromethyl-4-methyl-1,3-pentadiene being the monomer of choice.
  • These compounds may generally be prepared by the pyrolysis of an appropriately substituted 2,5-dihydro-thiophene-1,1-dioxide.
  • the preparation of 2-chloromethyl-4-methyl-1,3-pentadiene involves the pyrolysis of 3-chloromethyl-5,5-dimethyl-2,5-dihydrothiophene-1, 1-dioxide, the dioxide being prepared by a multistep sequence involving the reduction of 3-carboethoxy-5,5-dimethyl-2, 5-dihydrothiophene with lithium aluminum hydride to the corresponding hydromethyl compound, subsequent chlorination with a mixture of triphenyl phosphine in carbon tetrachloride and then oxidation of the chloromethyl compound with m-chloroperbenzoic acid.
  • the monomer charge suitable for use in the process of the present invention may further comprise a conjugated diolefin having from 4 to 8 carbon atoms in an amount of from about 1 ⁇ 10 -2 moles to about 1 ⁇ 10 -1 moles per mole of isobutylene.
  • a conjugated diolefin having from 4 to 8 carbon atoms in an amount of from about 1 ⁇ 10 -2 moles to about 1 ⁇ 10 -1 moles per mole of isobutylene.
  • the conjugated diolefin is isoprene.
  • the initiator suitable for use in the process disclosed herein has the formula ##STR6## wherein each R 4 may be the same of different and is an alkyl, aryl, or aralkyl group of 1 to 8 carbon atoms, Y is a carboxyl, alkoxyl, hydroxyl, halogen, hydroperoxide, peroxide or peroxy ester group and n is a positive whole number from 1 to 3 and the initiator is used in an amount of from about 1 ⁇ 10 -5 to about 1 ⁇ 10 -3 moles per mole of isobutylene.
  • Suitable initiators include 1,4-di(2-methoxy-2-propyl) benzene, 1,3,5-tri(2-methoxy-2-propyl) benzene, 1,4-di(2-chloro-2-propyl) benzene, 1,3,5-tri(2-chloro-2-propyl) benzene, 2,6-dichloro2,4,4,6-tetramethylheptane, 1,4-di(2-hydroxyl-2-propyl) benzene, 2,6-dihydroxyl-2,4,4,6-tetramethylheptane, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, 2,5-dimethyl-2,5-di(t-butylperoxy) hexyne-3, 2,5-di(hydroperoxy)-2,5-dimethylhexane, 2,7-di(hydroperoxy)-2, 7-di
  • Lewis acids are suitable for use in the process disclosed herein.
  • Non-limiting examples include boron trichloride, boron trifluoride, aluminum trichloride, stannic tetrachloride, titanium tetrachloride, antimony pentafluoride and vanadium tetrachloride, with the Lewis acids of preference being boron trichloride and titanium tetrachloride.
  • the amount of Lewis acid used relative to the amount of the initiator is not particularly critical. However, in order to be able to achieve more readily a polymer of the desired molecular weight, it is preferred that the mole amount of Lewis acid used is equal to or greater than the mole amount of the initiator used. Generally, it is preferred to use from about 1 ⁇ 10 -4 to about 5 ⁇ 10 -2 moles of a Lewis acid per mole of isobutylene.
  • the Lewis acid is employed as a solution in a low freezing non-complex forming solvent selected from the group consisting of C 1 to C 4 halogenated hydrocarbons.
  • a low freezing non-complex forming solvent selected from the group consisting of C 1 to C 4 halogenated hydrocarbons.
  • the solvent is selected from one of methyl chloride and methylene chloride.
  • the inert organic solvents suitable for use in the commercial butyl rubber polymerizations mentioned previously are also suitable for use as the solvent for the monomer charge and the initiator in the process of the present invention.
  • Preferred inert organic solvents o include C 1 to C 4 halogenated hydrocarbons and mixtures thereof, C 5 to C 8 aliphatic hydrocarbons, C 5 to C 8 cyclic hydrocarbons, mixtures of one or more said halogenated hydrocarbons and one or more of said aliphatic hydrocarbons and mixtures of one or more said halogenated hydrocarbons and one or more of said cyclic hydrocarbons.
  • the inert organic solvent is selected from the group consisting of methyl chloride, methylene chloride, hexane and cyclopentane and mixtures thereof.
  • a suitable reaction vessel first be charged with the isobutylene and the conjugated diolefin bearing an allylic halide moiety (and the conjugated diolefin having from 4 to 8 carbon atoms if it forms part of the monomer charge), the initiator and the inert organic solvent (if used) at a temperature of from about -90° C. to about -10° C.
  • the polymer produced according to the process disclosed herein may be recovered by conventional techniques used to recover rubbery polymers. Such techniques include for the higher molecular weight polymers, contacting the polymer solution or slurry with copious amounts of hot water thereby flashing the inert organic solvent and any unreacted monomer. The polymer-hot water slurry may then be passed through a tunnel dryer or drying extruder.
  • the polymer is recovered by (i) contacting the polymer solution or slurry with steam or by applying a vacuum to the polymer solution or slurry to flash off the solvent and any unreacted monomer; (ii) extracting acidic impurities and any remaining high boiling diluents with methanol; and (iii) drying the purified polymer to remove traces of methanol.
  • the polymer solution is contacted with excess water to remove inorganic residues, the solution is dried and the inert organic solvent is then removed, as by evaporation.
  • the products produced according to the process described herein are polymers bearing allylic halide functionality analogous to halogenated butyl rubbers. Evidence for the formation of such polymers is afforded by NMR spectroscopy. As an illustration the 250 MH z 1 H NMR spectrum of the product obtained upon the copolymerization of isobutylene with 2-chloromethyl-4-methyl-1, 3-pentadiene exhibits a number of signals that can be attributed to two different structures being present in the polymer.
  • a singlet at 3.95 ppm can be attributed to the methylene protons attached to the same carbon atom as the chlorine atom PIB(C1CH 2 )C ⁇ CH PIB and a singlet at 5.3 ppm can be attributed to a single olefinic proton PIB(C1Ch 2 )C ⁇ CH PIB suggesting that the major structure in the copolymer arises from the 1,4-addition of 2-chloromethyl-4-methyl-1, 3-pentadiene monomer to the polyisobutylene cation.
  • a minor structure in the copolymer appears to arise from 1,2-addition of the trisubstituted olefinic bond of the 2-chloromethyl-4-methyl-1, 3-pentadiene monomer to the polyisobutylene cation as a singlet at 4.0 ppm can be attributed to the methylene protons attached to the same carbon as the chlorine atom PIB(C1 CH 2 )C ⁇ CH 2 and the singlet at 5.2 ppm can be attributed to two olefinic protons attached to the same carbon atom of the olefinic bond PIBC(C1CH 2 )C ⁇ CH 2 .
  • conjugated diolefins such as 2-chloromethyl-4-methyl-1,3-pentadiene wherein the olefinic bond that does not bear the allylic halide moiety bears at least two methyl substituents, that is at least both of R 1 and R 2 are methyl groups
  • isobutylene upon copolymerization with isobutylene are incorporated into the copolymer to a greater extent relative to conjugated diolefins such as 2-chloromethy-1,3-butadiene wherein the olefinic bond that does not bear the allylic halide moiety, is a terminal olefinic bond, in part because of the stabilization afforded the intermediate allylic cation by the methyl substituents.
  • 2-chloromethyl-4-methyl-1,3-pentadiene, 2-bromomethyl-4-methyl-1,3-pentadiene and 2-chloromethyl-3,4-dimethyl-1,3-pentadiene are the monomers preferred for copolymerization with isobutylene
  • 2-chloromethyl-4-methyl-1,3-pentadiene is the monomer of choice for the production of a chlorinated copolymer analogous to chlorinated butyl rubber.
  • 3-Bromomethyl-2,5-dihydrothiophene-1,1-dioxide (22.0 g, 0.10 mol) was placed in a 100 ml round-bottomed flask which was connected to a short-path still and the system was evacuated to 1.5 mm/Hg pressure. The flask was lowered into an oilbath which had been preheated to a temperature of about 170° to about 190° C. while the receiver was cooled in a liquid nitrogen bath. After about 15 minutes the vacuum was released and the receiving flask was warmed to ambient temperature in a fume hood to allow the sulphur dioxide to escape.
  • the methylene chloride layer was dried over anhydrous magnesium sulphate, filtered and concentrated to afford a mixture of the desired product and m-chlorobenzoic acid.
  • the desired product, the sulphone was purified by column chromatography (support silica gel 60, 70-230 mesh; column size: 40 ⁇ 400 mm; eluants: ether-petroleum ether (35°-60° C.) mixtures; the eluant being changed from 20 percent ether to 40 percent ether in the petroleum ether. After two chromatographic passes, 3-chloromethyl-5, 5-dimethyl-2, 5-dihydrothiophene-1, 1-dioxide was obtained. 17.2 g (80 percent yield).
  • the copolymerizations were quenched by the addition of methanol (5 ml) to each test tube.
  • the resultant copolymers were recovered by first partially removing the solvent under reduced pressure and then coagulating copolymers by the addition of methanol.
  • the copolymerization parameters and the physical properties of the resultant copolymers are provided in Table I.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US08/014,295 1993-02-05 1993-02-05 Process for preparing halobutyl-type polymer Expired - Fee Related US5342908A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US08/014,295 US5342908A (en) 1993-02-05 1993-02-05 Process for preparing halobutyl-type polymer
CA002113891A CA2113891A1 (en) 1993-02-05 1994-01-20 Halogenated butyl rubber analogue
DE69424809T DE69424809T2 (de) 1993-02-05 1994-01-24 Verfahren zur Herstellung von halogeniertem Butylkautschuk
EP94100941A EP0609737B1 (de) 1993-02-05 1994-01-24 Verfahren zur Herstellung von halogeniertem Butylkautschuk
JP6027600A JPH06287234A (ja) 1993-02-05 1994-02-01 ハロゲン化ブチルゴムの製造方法
US08/213,658 US5473029A (en) 1993-02-05 1994-03-15 Process for preparing butyl polymers with allylic halide functionality

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/014,295 US5342908A (en) 1993-02-05 1993-02-05 Process for preparing halobutyl-type polymer

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US08/213,658 Continuation-In-Part US5473029A (en) 1993-02-05 1994-03-15 Process for preparing butyl polymers with allylic halide functionality

Publications (1)

Publication Number Publication Date
US5342908A true US5342908A (en) 1994-08-30

Family

ID=21764618

Family Applications (2)

Application Number Title Priority Date Filing Date
US08/014,295 Expired - Fee Related US5342908A (en) 1993-02-05 1993-02-05 Process for preparing halobutyl-type polymer
US08/213,658 Expired - Fee Related US5473029A (en) 1993-02-05 1994-03-15 Process for preparing butyl polymers with allylic halide functionality

Family Applications After (1)

Application Number Title Priority Date Filing Date
US08/213,658 Expired - Fee Related US5473029A (en) 1993-02-05 1994-03-15 Process for preparing butyl polymers with allylic halide functionality

Country Status (5)

Country Link
US (2) US5342908A (de)
EP (1) EP0609737B1 (de)
JP (1) JPH06287234A (de)
CA (1) CA2113891A1 (de)
DE (1) DE69424809T2 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5418303A (en) * 1993-09-03 1995-05-23 Exxon Chemical Patents Inc. Carbocationic catalysts and process for using said catalysts
US6274689B1 (en) 1998-10-07 2001-08-14 Exxon Chemical Patents, Inc. Random isomonoolefin/allyl styrene copolymers and functionalized derivatives thereof
US20060173217A1 (en) * 2005-01-28 2006-08-03 Abbas Kadkhodayan Seal swell agent and process therefor
US20130203943A1 (en) * 2010-03-24 2013-08-08 Lanxess International Sa Process for the production of water and solvent-free halobutyl rubbers

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19627529A1 (de) * 1996-07-09 1998-01-15 Bayer Ag Neue, vanadiumhaltige Initiatorsysteme für die (Co)polymerisation von Isoolefinen
US6268446B1 (en) 1997-12-04 2001-07-31 The University Of Western Ontario Initiators for carbocationic polymerization of olefins
US6344538B1 (en) * 1998-08-24 2002-02-05 Iowa State University Research Foundation, Inc. Functionalized diene monomers and polymers containing functionalized dienes and methods for their preparation
US8026325B2 (en) 2006-08-23 2011-09-27 Lanxess Inc. Co-polymerization of an isoolefin with a halogenated co-monomer
CA2593511C (en) * 2006-08-23 2015-05-19 Lanxess Inc. Co-polymerization of an isoolefin with a halogenated co-monomer

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3067182A (en) * 1959-08-03 1962-12-04 Dow Chemical Co Isopropenylbenzyl chloride and polymers thereof
US3299020A (en) * 1963-12-24 1967-01-17 Exxon Research Engineering Co Olefin-allyl halide copolymer
US3700648A (en) * 1968-09-30 1972-10-24 Sumitomo Chemical Co Method for producing alternating copolymers
US4074035A (en) * 1975-04-22 1978-02-14 Exxon Research & Engineering Co. Halomethylated aromatic interpolymers
US4943616A (en) * 1988-07-26 1990-07-24 Polysar Limited Living cationic polymerization process

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58149933A (ja) * 1982-03-02 1983-09-06 Japan Synthetic Rubber Co Ltd 高弾性ゴム組成物
CA1336281C (en) * 1988-07-26 1995-07-11 Munmaya Kumar Mishra Polymerization process and catalyst system therefor
EP0471248B1 (de) * 1990-08-16 1997-02-19 BASF Aktiengesellschaft Verfahren zur Herstellung von Kohlenwasserstoffen und Polymeren mit allylischen Chloridendgruppen
US5260383A (en) * 1991-04-17 1993-11-09 Polysar Rubber Corporation Polyisobutylene based block copolymers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3067182A (en) * 1959-08-03 1962-12-04 Dow Chemical Co Isopropenylbenzyl chloride and polymers thereof
US3299020A (en) * 1963-12-24 1967-01-17 Exxon Research Engineering Co Olefin-allyl halide copolymer
US3700648A (en) * 1968-09-30 1972-10-24 Sumitomo Chemical Co Method for producing alternating copolymers
US4074035A (en) * 1975-04-22 1978-02-14 Exxon Research & Engineering Co. Halomethylated aromatic interpolymers
US4943616A (en) * 1988-07-26 1990-07-24 Polysar Limited Living cationic polymerization process

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Sadykh Zade et al in Dokl.Akad.Nauk Azerb. SSR 1968, 24(6) pp. 20 23 (Chem. Abstr. 70, 20786j). *
Sadykh-Zade et al in Dokl.Akad.Nauk Azerb. SSR 1968, 24(6) pp. 20-23 (Chem. Abstr. 70, 20786j).

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5418303A (en) * 1993-09-03 1995-05-23 Exxon Chemical Patents Inc. Carbocationic catalysts and process for using said catalysts
US6274689B1 (en) 1998-10-07 2001-08-14 Exxon Chemical Patents, Inc. Random isomonoolefin/allyl styrene copolymers and functionalized derivatives thereof
US20060173217A1 (en) * 2005-01-28 2006-08-03 Abbas Kadkhodayan Seal swell agent and process therefor
US7485734B2 (en) 2005-01-28 2009-02-03 Afton Chemical Corporation Seal swell agent and process therefor
US20130203943A1 (en) * 2010-03-24 2013-08-08 Lanxess International Sa Process for the production of water and solvent-free halobutyl rubbers
US20150183894A1 (en) * 2010-03-24 2015-07-02 Lanxess International Sa Process for the production of water and solvent-free halobutyl rubbers
US10017588B2 (en) * 2010-03-24 2018-07-10 Arlanxeo Deutschland Gmbh Process for the production of water and solvent-free halobutyl rubbers

Also Published As

Publication number Publication date
DE69424809D1 (de) 2000-07-13
EP0609737A2 (de) 1994-08-10
EP0609737A3 (de) 1994-12-28
DE69424809T2 (de) 2000-10-12
JPH06287234A (ja) 1994-10-11
CA2113891A1 (en) 1994-08-06
EP0609737B1 (de) 2000-06-07
US5473029A (en) 1995-12-05

Similar Documents

Publication Publication Date Title
EP0509357B1 (de) Blockcopolymeren auf der Basis von Polyisobutylen
US4870144A (en) Process for producing an isobutylene polymer having functional terminal end groups
JPH02150408A (ja) パラ―アルキルスチレン／イソオレフィン共重合体
US5342908A (en) Process for preparing halobutyl-type polymer
EP0579058B1 (de) Butylkautschuk mit bimodaler Molekulargewichtsverteilung
KR100893444B1 (ko) 높은 이중 결합 함량을 가진 할로겐화된, 고 분자량,비-겔 상태 이소부텐 공중합체
JP3010575B2 (ja) イソブテン−シクロジエンコポリマーの製法
CN116410415B (zh) 一种溴化宽分布三臂支化丁基橡胶的制备方法
US5543479A (en) Process for the production of polyisoolefins
US4138441A (en) Synthesis of substituted cyclopentadienes and cyclopentadiene-functionalized polymers
US4316978A (en) Synthesis of substituted cyclopentadienes and cyclopentadiene-functionalized polymers
US3511821A (en) Terpolymers of isobutylene-methylcyclopentadiene and a crosslinking agent
IT201800005841A1 (it) Procedimento per la preparazione di copolimeri random butadiene-isoprene ad elevato contenuto di unita’ 1,4-cis
US4246373A (en) Synthesis of substituted cyclopentadienes and cyclopentadiene-functionalized polymers
CA2593511C (en) Co-polymerization of an isoolefin with a halogenated co-monomer
KR20010075583A (ko) 이소모노올레핀/알릴 스티렌 랜덤 공중합체 및 그의관능화된 유도체
US4210737A (en) Synthesis of substituted cyclopentadienes and cyclopentadiene-functionalized polymers
US4378456A (en) Terpolymers of ethylene, butadiene and isoprene and a process for their preparation
US8026325B2 (en) Co-polymerization of an isoolefin with a halogenated co-monomer
US2462703A (en) Copolymers of multiolefins with vinyl ethers and method of making same
US2977347A (en) Polymerization of olefins with molybdenum pentachloride catalyst
US3850894A (en) Procedure for the production of polymers and copolymers of isobutylene and polymers obtained
KR100210705B1 (ko) 이소부텐-시클로디엔 공중합체의 제조방법
JPH10298241A (ja) イソオレフイン、共役ジオレフイン及び、１個又は複数個の不飽和結合を有する有機化合物の新規なターポリマー
KR19990060041A (ko) 가공성이 개선된 이소부텐-시클로디엔 공중합체의 제조방법

Legal Events

Date Code Title Description
AS Assignment

Owner name: POLYSAR RUBBER CORP., CANADA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:OSMAN, AKHTAR;REEL/FRAME:006732/0593

Effective date: 19930122

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20020830

AS Assignment

Owner name: LANXESS INC., CANADA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BAYER INC.;REEL/FRAME:017186/0200

Effective date: 20040701